Nitration chlorotoluenes

The isomer proportions for the nitration of the chlorotoluenes, to be expected from the additivity principle, have been calculated from the partial rate factors for the nitration of toluene and chlorobenzene and compared with experimental results for nitration with nitric acid at o °C. The calculated values are indicated in brackets beside the experimental values on the following structural formulae. In general, it can be... 

Here, and with the chlorotoluenes, the precise values for the calculated figures depend on the values adopted for the partial rate factors in the mono-substituted compounds. These and the relative rates do depend slightly on conditions. As has been pointed out several times previously, comparisons with benzene for nitration in sulphuric acid have to be made with care. 

The side-chain chlorine contents of benzyl chloride, benzal chloride, and benzotrichlorides are determined by hydrolysis with methanolic sodium hydroxide followed by titration with silver nitrate. Total chlorine determination, including ring chlorine, is made by standard combustion methods (55). Several procedures for the gas chromatographic analysis of chlorotoluene mixtures have been described (56,57). Proton and nuclear magnetic resonance shifts, characteristic iafrared absorption bands, and principal mass spectral peaks have been summarized including sources of reference spectra (58). Procedures for measuring trace benzyl chloride ia air (59) and ia water (60) have been described. 

Synonym Gamma-Chloropropylene Oxide 3-Chloro-1,2-Propylene Oxide Chlorosulfonic Acid Chlorothene Chiorotoluene, Alpha Alpha-Chlorotoluene Omega-Chlorotoluene Chlorotrifluoroethylene Chlorotrimethylsilane Chlorsulfonic Acid Clilorylen Clip Chromic Acid Chromic Anhydride Chromic Oxide Chromium (VI) Dioxychloride Chromium Oxychloride Chromium Trioxide Chromyl Chloride Cianurina Citric Acid Citric Acid, Diammonium Salt Clarified Oil Clorox Cc Ral Coal Tar Oil Cobalt Acetate Cobalt Acetate Tetrahydrate Cobalt (II) Acetate Cobalt Chloride Cobalt (II) Chloride Cobaltous Acetate Cobaltous Chloride Cobaltous Chloride Dihydrate Cobaltous Chloride Hexahydrate Cobaltous Nitrate Cobaltous Nitrate Hexahydrate Cobaltous Sulfate Heptahydrate Cobalt Nitrate Cobalt (II) Nitrate Cobalt Sulfate Compound Name Epichlorohydrin Epichlorohydrin Chlorosulfonic Acid Trichloroethane Benzyl Chloride Benzyl Chloride Benzyl Chloride Trifluorochloroethylene Trimethylchlorosilane Chlorosulfonic Acid Trichloroethylene Cumene Hydroperoxide Chromic Anhydride Chromic Anhydride Chromic Anhydride Chromyl Chloride Chromyl Chloride Chromic Anhydride Chromyl Chloride Mercuric Cyanide Citric Acid Ammonium Citrate Oil Clarified Sodium Hypochlorite Coumaphos Oil Coal Tar Cobalt Acetate Cobalt Acetate Cobalt Acetate Cobalt Chloride Cobalt Chloride Cobalt Acetate Cobalt Chloride Cobalt Chloride Cobalt Chloride Cobalt Nitrate Cobalt Nitrate Cobalt Sulfate Cobalt Nitrate Cobalt Nitrate Cobalt Sulfate... 

AcadAboensis, MathPhys 14, No 3, 9 pp( 1943) ChemZtr 1943 II, 1268-69 CA 38, 5492(1944) [By nitration of 3-chloro-p-cymene and repeated crystn from AcOH, there was obtd 2,4-Dinitro 3 chlorotoluene (qv), mp 90 90.5° this compd also resulted by reaction of 3-chlorotoluene with fuming HN03 St coned H2S04 and crystn from 85% AcOH. This compd is reported identical with the supposed 3,5 Dinitro 2 chloro 4 methylacetophenone or N. Ganguly R. LeFevre, CA 28, 5416(1934). Q M report that the latter compd other derivs of G LeF have not been prepd and should be removed from the chemical literature] 2,4,6-Trlnltro-3-chlorotoluene, (02N)3(C1).-C6H.CH3 mw 261.58, N 16.07% wh ndls (from benz + petr eth), mp 148.5-151° readily sol in AcOH, benz, acet or chlf less sol in ale, eth or petr eth was prepd by nitrating, with mixed acids, either 2,4-dinitro 5 chloro-toluene or 3 chlorotoluene(Refs 1 3) and by... 

Predicted and Observed Product Distributions for the Nitration of the Chlorotoluenes... 

Trlnitro-3-chlorotoluene, (02N)3(C1).-CgH.CH3 mw 261.58, N 16.07% wh ndls (from benz + petr eth), mp 148<5 151° readily sol in AcOH, benz, acet or chlf less sol in ale, eth or petr eth was prepd by nitrating, with mixed acids, either 2,4-dinitro-5-chloro-toluene or 3-chlorotoluene(Refs 1 3) and by... 

The nitration of chlorobenzene, dichlorobenzene, and chlorotoluene leads to substances of considerable value in dye chemistry in that nitro groups in position 2- and 4- relative to chlorine having an activating effect [11]. 

Derivation From o-chlorotoluene-p-sulfomc acid by nitration and subsequent reduction. 

Azoic Diazo Component 32, produced by nitration of >-chlorotoluene followed by reduction of the resulting 4-chloro-2-nitrotoluene and Azoic Diazo Component 34, produced by nitration of o-benzenesulfonotoluidide followed by hydrolysis. Va.ria.mine Blue B the half sulfate [6254-98 4] of (90), ie, Azoic Diazo Component 35 used for dark blue or green shades is marketed as the free base or half sulfate. It is produced by condensation of anisidine with 2-chloro-5-nitrobenzenesulfonic acid, reduction, and desulfonation of the resulting 5-amino-2- anisidinobenzenesulfonic acid. 

In comparison with alkyl halogenides, halides bound to aromatic nuclei are less reactive, and, unless activated by the presence of other substituents (for example, reactive chlorine in 2,4-dinitrochlorobenzene), nucleophilic substitution reactions cannot be used for their identification. For the identification, electrophilic substitution reactions on aromatic nuclei are used predominantly, such as nitration and chlorosulfonation. Only in exceptional and special cases are other procedmes used [preparation of Grignard reagent and the conversion to anilides (12) preparation of addition compounds with picric acid-chloronaphthalenes, see p. 127 oxidation of side chains-oxidation of chlorotoluene to the corresponding chlorobenzoic acid, see p. 129]. 

Nitration of o-chlorotoluene yields a mixture of four chloronitrotoluene isomers. Considering the directing influences of the chlorine atom and methyl group, and their effects on reactivity, explain why a mixture results. 

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